CN112020582A - Pollution inhibitor composition - Google Patents

Pollution inhibitor composition Download PDF

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CN112020582A
CN112020582A CN202080000256.6A CN202080000256A CN112020582A CN 112020582 A CN112020582 A CN 112020582A CN 202080000256 A CN202080000256 A CN 202080000256A CN 112020582 A CN112020582 A CN 112020582A
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group
drying
resin
siloxane compound
composition according
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CN112020582B (en
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关谷宏
游佐和之
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Maintech Co Ltd
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Maintech Co Ltd
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F5/00—Dryer section of machines for making continuous webs of paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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    • C08G77/04—Polysiloxanes
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    • C08G77/04—Polysiloxanes
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    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract

The invention provides a pollution preventing agent composition which can effectively prevent resin pollution of a drying part. The present invention is a contamination preventive composition for preventing resin contamination in a drying section of a papermaking process, comprising: a linear polysiloxane compound and a cyclic siloxane compound represented by the following formula (1). [ in the formula (1), the substituent R1In the same molecule, a hydrogen atom, an alkyl group, a methylphenyl group, a polyether group, a higher fatty acid ester group, an amino group-modifying group, a carboxyl group,an epoxy-modified group, a carboxyl group, a phenol group, a mercapto group, a carbinol group or a methacrylic group, wherein the number n of repeating units of the siloxane unit represents an integer of 20 to 1430.]
Figure DDA0002409029990000011

Description

Pollution inhibitor composition
Technical Field
The present invention relates to a stain inhibitor composition, and more particularly, to a stain inhibitor composition capable of effectively preventing the occurrence of resin staining of a dry part.
Background
The paper making process in a paper machine generally includes a wire section, a press section, a drying section, and a winding section. In the wire part, pulp dispersed in water is carried on a wire (wire) for papermaking, and excess water is naturally filtered to obtain wet paper; in the press section, the wet paper is passed between a pair of press rolls, and is pressed by the press rolls via a felt, so that the water in the wet paper is transferred to the felt, thereby dewatering the wet paper; in the drying section, drying the wet paper by bringing the wet paper passed through the press section into contact with a heated drying roll to obtain paper; in the winding section, the paper is wound around a rod called a reel.
The drying part includes a cylindrical drying roll for heating and drying the wet paper, a canvas roll for pressing the wet paper against the drying roll, a canvas roll for guiding the canvas roll, a calender roll for adjusting smoothness and thickness of the dried wet paper, and a semi-dry calender roll for slowly adjusting smoothness and thickness of the dried wet paper. Since the devices directly or indirectly contact the wet paper, if resin adheres to the surfaces of the devices, the resin is transferred to the wet paper to contaminate the wet paper, which may significantly reduce the yield.
The resin (pitch) is a sticky contaminant formed by a resin component contained in wood or old paper as a raw material of paper.
In contrast, a stain inhibitor composition is known, which can prevent resin staining by applying the stain inhibitor composition to a drying section, and which contains a silicone compound.
For example, as the above-mentioned stain inhibitor composition, the following stain inhibitor compositions are known: contains a polysiloxane compound having a predetermined chemical structural formula, and the number of amino-modified groups per 1 molecule of the polysiloxane compound is 0.5 to 5 (see, for example, patent document 1).
Further, there is known a stain inhibitor composition comprising a low-molecular-weight polysiloxane compound having a predetermined chemical structural formula and a high-molecular-weight polysiloxane compound having a predetermined chemical structural formula, wherein the kinematic viscosity of the low-molecular-weight polysiloxane compound at 25 ℃ is 10 to 300mm2(s) the kinematic viscosity of the high molecular weight polysiloxane compound at 25 ℃ is 40 to 90000mm2And/s, the number of modifying groups per 1 molecule of the low-molecular-weight polysiloxane compound is 0.1 to 3.0, the number of modifying groups per 1 molecule of the high-molecular-weight polysiloxane compound is 1.0 to 10, and the number m of repeating units of the polysiloxane unit in the low-molecular-weight polysiloxane compound and the number n of repeating units of the polysiloxane unit in the high-molecular-weight polysiloxane compound satisfy a relationship of 2 m.ltoreq.n (see, for example, patent document 2).
The contamination preventive composition can substantially prevent the occurrence of resin contamination in the drying section. The present invention corresponds to an invention in which the above invention is improved.
Documents of the prior art
Patent documents:
patent document 1: japanese patent No. 4868628
Patent document 2: japanese patent No. 4868629
Disclosure of Invention
Problems to be solved by the invention
However, the stain inhibitor compositions described in patent documents 1 and 2 have an effect of preventing the occurrence of resin stains by dispersing a resin, but the effect is not sufficient. That is, the dispersion degree of the resin is insufficient, and the resin not dispersed may adhere to the drying section again.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a contamination preventive composition capable of effectively preventing resin contamination of a drying section from occurring.
Means for solving the problems
The present inventors have intensively studied the above problems and found that a cyclic siloxane compound can be used as a component for effectively dispersing a resin.
Further, the present inventors have found that the above problems can be solved by adding a cyclic siloxane compound to a stain inhibitor composition, and have completed the present invention.
The invention of claim 1 is a stain inhibitor composition for preventing resin staining in a drying section of a paper making process, comprising: a linear polysiloxane compound and a cyclic siloxane compound represented by the following formula (1).
[ CHEM 1 ]
Figure BDA0002409029970000031
[ in the formula (1), the substituent R1The siloxane compound is characterized in that the siloxane compound represents a hydrogen atom, an alkyl group, a methylphenyl group, a polyether group, a higher fatty acid ester group, an amino modified group, an epoxy modified group, a carboxyl group, a phenol group, a mercapto group, a carbinol group or a methacrylic group in the same molecule, and the number n of the repeating units of the siloxane unit represents an integer of 20-1430.]
The invention of claim 2 is the composition of claim 1, wherein the substituent R is the same as the substituent R1At least one of which is an amino-modified group represented by the following formula (2).
[ CHEM 2 ]
Figure BDA0002409029970000032
[ in the formula (2), the substituent R2And a substituent R3Each independently represents an alkylene group having 1 to 6 carbon atoms, and the number m of repeating units of the aminoalkylene unit represents an integer of 0 to 2.]
The invention according to claim 3 is the stain inhibitor composition according to claim 1 or 2, wherein the cyclic siloxane compound is at least one selected from the group consisting of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
The invention of claim 4 is the stain inhibitor composition according to any one of claims 1 to 3, wherein the amount of the cyclic siloxane compound is 15ppm to 20000 ppm.
The invention according to claim 5 is the antifouling composition according to any one of claims 1 to 4, wherein the weight ratio of the cyclic siloxane compound to the polysiloxane compound to be compounded is 1:5 to 50000.
The invention according to claim 6 is the antifouling composition according to any one of claims 1 to 5, wherein the antifouling composition is an emulsion further comprising an emulsifier and water, and the median particle diameter of the emulsion is 0.01 to 5.0 μm.
The invention according to claim 7 is the antifouling composition according to any one of claims 1 to 6, wherein the antifouling composition is applied to a drying roll made of cast iron or a canvas made of polyester in a drying section, and an absolute value of Zeta potential is 10 to 90.
The invention according to claim 8 is the antifouling composition according to any one of claims 1 to 7, wherein the antifouling composition is applied to a drying roll made of cast iron in a drying section, has a surface tension of 65mN/m or less, and has a contact angle with the drying roll of 80 ° or less.
The invention according to claim 9 is the antifouling composition according to any one of claims 1 to 8, wherein the surface tension of the canvas made of polyester applied to the drying section is 65mN/m or less, and the contact angle with the canvas is 80 ° or less.
ADVANTAGEOUS EFFECTS OF INVENTION
Since the stain inhibitor composition of the present invention contains the linear polysiloxane compound represented by the above formula (1), when the composition is applied to a dry part (for example, a dry roll), a coating film can be formed on the dry part, and adhesion of resin can be inhibited (resin adhesion preventing effect). This can prevent resin contamination of the drying section.
In addition, since the stain inhibitor composition further contains a cyclic siloxane compound, the resin can be efficiently dispersed (resin dispersion effect). That is, the cyclic siloxane compound efficiently disperses the resin whose adhesion is inhibited, thereby preventing not only the initial adhesion of the resin but also the reattachment of the resin. In view of sufficiently exhibiting the effect of dispersing the resin, the amount of the cyclic siloxane compound is preferably within the above range.
Accordingly, the contamination preventive composition of the present invention can effectively prevent the occurrence of resin contamination in the dry part.
In the stain inhibitor composition of the present invention, when the substituent R is present in the same molecule1When at least one of the amino groups is an amino-modified group represented by the above formula (2), the film holding force of the film formed of the linear polysiloxane compound can be improved. That is, the coating film can be easily fixed to the drying section.
In the stain inhibitor composition of the present invention, when the cyclic siloxane compound is at least one selected from the group consisting of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, the effect of dispersing the resin can be reliably exhibited.
In the stain inhibitor composition of the present invention, the ratio by mass of the silicone compound and the cyclic siloxane compound to be blended is preferably within the above range. In this case, the resin adhesion preventing effect and the resin dispersing effect can be well balanced. That is, a state in which the resin is adhered and cannot be dispersed or a state in which the resin is dispersed with delay can be suppressed.
In the stain inhibitor composition of the present invention, when the stain inhibitor composition is an emulsion further containing an emulsifier and water, the median particle diameter of the emulsion is set to be in the above range, whereby even a mixture of the polysiloxane compound and the cyclic siloxane compound can achieve good dispersion stability of both. Accordingly, the silicone compound and the cyclic siloxane compound can be uniformly applied to the drying section while being maintained at a predetermined ratio.
In the stain inhibitor composition of the present invention, when the absolute value of Zeta potential is within the above range, there is an advantage that the stain inhibitor composition can be easily fixed to the surface of a drying roll made of cast iron or the surface of a canvas made of polyester by the action of electricity. Accordingly, it is possible to suppress the occurrence of a situation in which the stain inhibitor composition applied to the drying roll is transferred to the wet paper brought into contact with the drying roll and is not substantially left on the drying roll, or the situation in which the stain inhibitor composition applied to the canvas is transferred to the wet paper brought into contact with the canvas and is not substantially left on the canvas.
In the stain inhibitor composition of the present invention, when the surface tension is within the above range, a coating film can be easily formed on the surface of the drying roll made of cast iron or the surface of the canvas made of polyester. This can further improve the effect of preventing adhesion of resin.
Further, since the resin is easily permeated, the resin dispersion effect can be improved.
In the stain inhibitor composition of the present invention, a coating film is easily formed on the surface of a drying roller made of cast iron by setting the contact angle with the drying roller to 80 ° or less.
Further, by setting the contact angle with the canvas made of polyester to 80 ° or less, a coating film is easily formed on the surface of the canvas.
This can further improve the effect of preventing adhesion of resin.
Drawings
Fig. 1 is a schematic view showing a dry end using the stain inhibitor composition of the present invention.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings as required. Unless otherwise noted, the positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings. Further, the dimensional scale of the drawings is not limited to the illustrated scale.
The stain inhibitor composition of the present invention can prevent a dry part from being contaminated with resin (hereinafter, simply referred to as "resin stain") by applying the composition to the dry part in a papermaking process.
Here, the drying section includes devices such as a drying roll, a canvas roll, a calender roll, and a semi-dry calender roll. Further, for details of the drying section, refer to the following.
The anti-fouling composition of the present invention contains a linear polysiloxane compound, a cyclic siloxane compound, an emulsifier, and water.
The stain inhibitor composition exerts a resin adhesion preventing effect by forming a coating film on the surface of the dry part from a silicone compound when applied to the dry part.
At this time, the coexisting cyclic siloxane compound exerts a resin dispersing effect.
Due to the above-mentioned effects, the resin contamination of the drying section can be effectively prevented from occurring by using the contamination preventive composition.
The stain inhibitor composition is an emulsion of an oily silicone compound and a cyclic silicone compound emulsified with aqueous water by an emulsifier.
Here, the median particle diameter of the emulsion is preferably 0.01 to 5.0. mu.m. In this case, even in the case of a mixture of the polysiloxane compound and the cyclic siloxane compound, both have excellent dispersion stability with time.
If the median particle diameter is less than 0.01 μm, the water resistance of the coating after the formation of the coating may be lower than when the median particle diameter is within the above range, and if the median particle diameter exceeds 5.0 μm, the emulsion stability may be lower than when the median particle diameter is within the above range.
The stain inhibitor composition preferably has a Zeta potential of-90 to-10 or, +10 to +90 when applied to a drying roll made of cast iron. That is, the absolute value is preferably 10 to 90. In this case, the drying roller is advantageously easily fixed to the surface of the drying roller by the action of electricity.
If the absolute value of the Zeta potential is less than 10, the adsorption of the stain inhibitor composition to the surface of the drying roll may be reduced and the emulsion stability may be reduced, as compared to when the Zeta potential is within the above range. When the absolute value of the Zeta potential exceeds 90, the adsorption of the stain inhibitor composition to the surface of the drying roll tends to be too high and the transfer of the stain inhibitor composition to the wet paper tends to be insufficient, as compared with the case where the Zeta potential is within the above range. As will be described later, by transferring an appropriate amount of the contamination preventive composition to the wet paper, the contamination preventive composition can be transferred again to the downstream side drying part in contact with the wet paper.
Similarly, the stain inhibitor composition preferably has a Zeta potential of-90 to-10, or, +10 to +90, when applied to a canvas made of polyester. That is, the absolute value is preferably 10 to 90. In this case, the canvas has an advantage of being easily fixed to the surface of the canvas by the electric action.
If the absolute value of the Zeta potential is less than 10, the adsorption of the stain inhibitor composition to the canvas surface may be reduced and the emulsion stability may be reduced, as compared to when the Zeta potential is within the above range. When the absolute value of the Zeta potential exceeds 90, the adsorption of the stain inhibitor composition to the canvas surface tends to be too high and the transfer of the stain inhibitor composition to the wet paper tends to be insufficient, as compared with the case where the Zeta potential is within the above range. As will be described later, by transferring an appropriate amount of the stain inhibitor composition to the wet paper, the stain inhibitor composition can be transferred again to the downstream side drying section in contact with the wet paper.
The surface tension (dynamic surface tension when the life time of the maximum bubble pressure method is 100 milliseconds) of the stain inhibitor composition applied to a drying roll made of cast iron is preferably 65mN/m or less. In this case, there is an advantage in that the fixing to the surface of the drying roller is easy.
When the surface tension exceeds 65mN/m, the coating film may not be sufficiently formed because the rate of formation of the coating film on the surface of the drying roller is reduced as compared with the case where the surface tension is within the above range.
The surface tension value is measured at 25 ℃ using an automatic dynamic surface tensiometer BP-D5 (synergetics interface science).
Similarly, when the stain inhibitor composition is applied to a canvas made of polyester, the surface tension (dynamic surface tension when the life time of the maximum bubble pressure method is 100 milliseconds) is preferably 65mN/m or less. In this case, there is an advantage that the canvas can be easily fixed to the surface.
Further, if the surface tension exceeds 65mN/m, the rate of formation of the coating on the canvas surface is reduced as compared with the case where the surface tension is within the above range, and therefore the coating may not be sufficiently formed.
When the stain inhibitor composition is applied to a drying roller made of cast iron, the contact angle with the drying roller is preferably 80 ° or less. In this case, the coating film can be instantaneously formed on the surface of the drying roller.
The contact angle is measured using DropMasterDMs-401 and a Teflon needle 18G at 25 ℃ and 50% humidity.
The cast iron used for measuring the contact angle may be the same as or different from the cast iron of the drying roll. But preferably both are ten point roughness averages (Rz): maximum height (Rmax) of 0.16 μm or less: 0.21 [ mu ] m or less, arithmetic average roughness (Ra): cast iron of 0.04 μm or less.
Similarly, when the stain inhibitor composition is applied to a canvas made of polyester, the contact angle with the canvas is preferably 80 ° or less. In this case, a coating can be instantaneously formed on the surface of the canvas.
The silicone compound in the antifouling composition is linear and is represented by the following formula (1).
[ CHEM 3 ]
Figure BDA0002409029970000081
In the polysiloxane compound represented by the formula (1), the substituent R1There can be used a hydrogen atom, an alkyl group, a methylphenyl group, a polyether group, a higher fatty acid ester group, an amino group-modifying group, an epoxy group-modifying group, a carboxyl group, a phenol group, a mercapto group, a methanol group, a methacrylic group and the like. In addition, the substituents R1They may be the same in the same molecule or different in the same molecule.
In addition, the stain inhibitor composition may be mixed with the substituent R1Different polysiloxane compounds.
Among them, the substituent R is preferable from the viewpoint of the holding power of the coating film on the surface of the drying roller1Is a methyl and/or amino modifying group, more preferably a substituent R1Contains a reactive amino group-modifying group in the same molecule.
Here, the epoxy-modified group may be an alkylene oxide group or an epoxy polyether group.
Further, the amino-modified group is represented by the following formula (2).
[ CHEM 4 ]
Figure BDA0002409029970000082
In the amino group-modifying group represented by the formula (2), the substituent R2And a substituent R3Each independently an alkylene group having 1 to 6 carbon atoms.
Among these, the substituent R in the amino-modified group is preferable from the viewpoint of the holding power of the coating film on the surface of the drying roller2And a substituent R3Each independently is an ethenyl or propenyl group.
Further, the substituent R is preferable from the viewpoint of the holding power of the coating film on the surface of the drying roller2And a substituent R3Are different alkylene radicals, in particular the substituents R being particularly preferred2Is propenyl, substituent R3Is a vinyl group.
In the amino-modified group represented by the formula (2), the number m of repeating units of the aminoalkylene unit is an integer of 0 to 2. It should be noted that ifWhen the number m of repeating units of the aminoalkylene unit is 0, the amino-modified group has no substituent R2。
If the number m of repeating units of the aminoalkylene unit exceeds 3, the film holding force on the surface of the drying roller may be reduced, and the effect of preventing adhesion of the resin may be reduced.
Among these, the number m of repeating units of the aminoalkylene unit in the amino-modified group is preferably 1.
In the stain inhibitor composition, the number of amino-modified groups per 1 molecule of the polysiloxane compound is preferably 0.5 to 5, more preferably 0.5 to 3, from the viewpoint of film holding power and resin stain preventing effect.
If the number of amino-modified groups is less than 0.5, the film holding force on the surface of the drying roller may be reduced and the effect of preventing adhesion of resin may be reduced, as compared with the case where the number of amino-modified groups is within the above range. When the number of the amino-modified groups exceeds 5, the ionic property is improved and the surface of the drying part is excessively accumulated, compared with the case where the number of the amino-modified groups is in the above range, so that there is a disadvantage that the tackiness of the surface of the drying part is increased and the resin is liable to adhere to the surface.
In the present specification, the "number of amino-modified groups per 1 molecule of the polysiloxane compound" refers to the average number of amino-modified groups contained per 1 molecule, and specifically, refers to the value obtained by dividing the total number of amino-modified groups by the number of molecules. That is, if the number of amino-modified groups per 1 molecule is 0.1, this means that the total number of amino-modified groups contained per 10 molecules is 1.
In the polysiloxane compound represented by the formula (1), the number n of repeating units of a siloxane unit is an integer of 20 to 1430, preferably 50 to 1000, and more preferably 100 to 800.
If the number n of repeating units of the siloxane unit is less than 20, it may be difficult to sufficiently form a coating film. If the number n of repeating units of the siloxane unit exceeds 1430, the polysiloxane compound having a high viscosity adheres to the surface of the drying part with tackiness, and the resin is liable to adhere to the surface.
The kinematic viscosity at 25 ℃ of the preferred silicone compounds is 20000mm2(ii) less than s, more preferably 10000mm2The ratio of the water to the water is less than s.
If the kinematic viscosity exceeds 20000mm2The viscosity/s is higher than that when the kinematic viscosity is in the above range, and the resin tends to adhere to the surface of the substrate.
In the stain inhibitor composition, the cyclic siloxane compound is a monomolecular compound in which siloxane units are linked to form a cyclic ring.
Specifically, the cyclic siloxane compound is preferably at least one selected from the group consisting of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, and more preferably has different substituents in the molecule.
Examples of the substituent include an alkyl group, a methylphenyl group, a polyether group, a higher fatty acid ester group, an amino group-modifying group, an epoxy group-modifying group, a carboxyl group, a phenol group, a mercapto group, a methanol group and a methacrylic group. A plurality of the same substituent may be provided in the same molecule, or a plurality of different substituents may be provided.
Among them, the substituent is preferably an amino-modified group. That is, it is preferable that the cyclic siloxane compound has an amino group-modifying group in addition to a methyl group in the molecule. Specifically, the cyclic siloxane compound is more preferably at least one selected from the group consisting of octamethylcyclotetrasiloxane having an amino-modifying group, decamethylcyclopentasiloxane having an amino-modifying group, and dodecamethylcyclohexasiloxane having an amino-modifying group.
In this case, the resin dispersion effect can be effectively exhibited.
Further, it is preferable that the substituent of the cyclic siloxane compound and the substituent R of the linear polysiloxane compound represented by the formula (1) coexist1The same is true.
In this case, the compatibility of the cyclic siloxane compound with the linear polysiloxane compound is good, and therefore the storage stability of the stain inhibitor composition is improved.
Further, it is more preferable that all of the following are contained as the cyclic siloxane compound: octamethylcyclotetrasiloxane having an amino-modifying group, decamethylcyclopentasiloxane having an amino-modifying group, and dodecamethylcyclohexasiloxane having an amino-modifying group.
In this case, it is preferable that octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane account for 70% or more of the total amount of the cyclic siloxane compound.
In the stain inhibitor composition, it is preferable to use a nonionic surfactant or an anionic surfactant as the emulsifier.
Among them, the emulsifier is preferably a nonionic surfactant, and particularly more preferably polyoxyethylene decyl ether, polyoxyethylene cetyl ether or polyoxyethylene stearyl ether.
In this case, not only the emulsion stability of the silicone compound can be improved, but also the discoloration of the paper can be suppressed. Further, when a colored paper such as a corrugated cardboard is produced by a paper machine, if a polyoxyethylene alkyl ether having a low molecular weight alkyl group is used as the emulsifier, there is a disadvantage that the color of the paper is peeled off and a stain is generated. However, when a polyoxyethylene alkyl ether having a decyl group, a hexadecyl group or an octadecyl group as an alkyl group is used as the emulsifier, discoloration can be suppressed.
In the stain inhibitor composition, the proportion of the polysiloxane compound is preferably 0.1 to 40% by mass, more preferably 2.0 to 20% by mass, from the viewpoint of preventing adhesion of the resin.
If the compounding ratio of the silicone compound is less than 0.1 mass%, the contamination preventive composition itself may be absorbed by the wet paper before the water in the contamination preventive composition evaporates, and a coating film may not be sufficiently formed, as compared with the case where the compounding ratio of the silicone compound is within the above range. If the compounding ratio of the silicone compound exceeds 40 mass%, the viscosity of the stain inhibitor composition itself may increase, making it difficult to uniformly spray the stain inhibitor composition on the surface of the drying section, and the viscosity may increase, tearing the paper, as compared to when the compounding ratio of the silicone compound is within the above range.
The amount of the cyclic siloxane compound to be incorporated in the anti-fouling agent composition is preferably 15ppm to 20000ppm, more preferably 80ppm to 10000ppm, and particularly preferably 100ppm to 1000ppm, from the viewpoint of sufficiently exerting the resin dispersion effect.
If the amount of the cyclic siloxane compound is less than 15ppm, the resin dispersion effect is insufficient as compared with the case where the amount is within the above range. If the amount of the cyclic siloxane compound is more than 20000ppm, the surface of the dry part is more likely to accumulate than when the amount is within the above range, and therefore, the tackiness of the surface of the dry part is increased, which is disadvantageous in that the resin is likely to adhere to the surface.
In the stain inhibitor composition, the mass ratio of the cyclic siloxane compound to the polysiloxane compound to be blended is preferably 1:5 to 50000 from the viewpoint of achieving a balance between the effect of preventing adhesion of the resin and the effect of dispersing the resin.
If the mass ratio of the polysiloxane compound to 1 part by mass of the cyclic siloxane compound is less than 5 parts by mass, the effect of preventing adhesion of the resin may be insufficient as compared with the case where the mass ratio is within the above range. If the mass ratio of the polysiloxane compound to 1 part by mass of the cyclic siloxane compound exceeds 50000 parts by mass, the resin dispersion effect may be insufficient as compared with the case where the mass ratio is within the above range.
In the stain inhibitor composition, the proportion of the emulsifier is preferably 0.05 to 0.4 part by mass, more preferably 0.1 to 0.2 part by mass, based on 1 part by mass of the silicone compound.
If the blending ratio of the emulsifier is less than 0.05 parts by mass, the emulsion stability may be insufficient as compared with the case where the blending ratio of the emulsifier is within the above range. If the compounding ratio of the emulsifier exceeds 0.4 parts by mass, there is a disadvantage that the degree of decolorization of paper is increased as compared with the case where the compounding ratio of the emulsifier is within the above range.
In addition to the above components, the stain inhibitor composition may contain additives such as chelating agents, pH adjusting agents, preservatives, viscosity adjusting agents, lubricants, wetting agents, dust-proofing agents, mold release agents, adhesives, surface modifiers, detergents, paper strength enhancers, sizing agents, retention aids, water-repelling agents, oil-repelling agents, anti-slip agents, and softening agents.
The lubricant may be a mineral oil such as a gear oil, a dryer oil, a turbine oil, or a main shaft oil, a vegetable oil such as coconut oil, linseed oil, castor oil, rapeseed oil, or corn oil, a paraffin such as liquid paraffin or isoparaffin, or a synthetic oil such as polyisobutylene, polybutene, maleic anhydride-modified polybutene, polyethylene wax, or microcrystalline wax.
Next, a method for producing the stain inhibitor composition of the present embodiment will be described.
The stain inhibitor composition in which the polysiloxane compound and the cyclic siloxane compound are emulsified can be obtained by adding water to the polysiloxane compound, the cyclic siloxane compound, and the emulsifier and stirring them.
The stirring may be suitably carried out by a mixer, a homogenizer, a mill, or the like.
Next, a method of using the stain inhibitor composition in the dry section will be described.
Fig. 1 is a schematic view showing a dry end using the stain inhibitor composition of the present invention.
As shown in fig. 1, the contamination preventive composition is used in the drying section D.
The drying section D includes: a wet paper W; a plurality of cylindrical drying rolls D1, D2, D3, D4, D5, D6, D7, and D8 (hereinafter referred to as "D1 to D8") for heating and drying the wet paper W; canvas K1 and K2 for pressing the wet paper against the drying rolls D1 to D8; a canvas roller KR for guiding the canvas K1, K2; a half-dry calender roll B for slowly adjusting smoothness and thickness of the dried wet paper W; and a calender roll C for adjusting smoothness and thickness of the dried wet paper W.
In the drying section D, the drying rollers D1 to D8 are made of cast iron.
The cast iron is obtained by casting an alloy containing iron as a main component and at least one selected from the group consisting of nickel, chromium, carbon, and silicon.
In the drying section D, the wet paper W is pressed against the surfaces of the rotating drying rolls D1 to D8 by the canvas K1 or K2. Thereby, the wet paper W is heated and dried while being attached to the drying rolls D1 to D8. Then, the wet paper W is nipped by the semi-dry calender roll B, and then the density of the wet paper W is increased by the calender roll C.
In the method of using the stain inhibitor composition, as shown in fig. 1, the stain inhibitor composition is directly applied to the drying rolls D1 to D8, canvas K1, K2, half-dry calender roll B, and calender roll C of the drying section D at the positions of arrows a, respectively.
At this time, the stain preventing agent composition applied to the drying section D is transferred to the wet paper W in contact with the drying section D, and since the wet paper W is further transported therefrom, the stain preventing agent composition can be transferred again to the drying section D on the downstream side in contact with the wet paper W. As described above, the resin contamination of the downstream side dryer section D can be prevented from occurring only by applying a sufficient amount of the contamination preventive composition to the upstream side dryer section D.
Here, the method of applying the antifouling composition is not particularly limited, and for example, a liquid spray method or a mist spray method using a spray nozzle or the like can be used.
Further, the spray nozzle may be slid in the paper width direction while spraying the stain inhibitor composition. By spraying the contamination preventive composition to the drying section, the occurrence of resin contamination is prevented.
In this case, it is preferable that the amount of the polysiloxane compound sprayed per unit area of the paper through which the stain inhibitor composition is passed is 10 μ g to 10000 μ g/m in terms of solid content2More preferably 30 to 1000. mu.g/m2。
If the spraying amount is less than 10 μ g/m2In comparison with the case where the spraying amount is within the above range, the stain inhibitor composition tends not to adhere to the surface of the drying section sufficiently and not to inhibit adhesion of the resin sufficiently. If the spraying amount exceeds 10000 mu g/m2In comparison with the case where the amount of spraying is within the above range, an excessive portion may be accumulated on the surface of the drying section, thereby causing resin inclusion, increased contamination, or clogging of the canvas.
The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments.
For example, the stain inhibitor composition of the present embodiment contains a linear polysiloxane compound, a cyclic siloxane compound, an emulsifier, and water, but the emulsifier and water are not essential.
In the stain inhibitor composition of the present embodiment, the stain inhibitor composition is applied to a drying roll in a drying section (see fig. 1), but the stain inhibitor composition is not limited to the drying section, and may be applied to canvas rolls, calender rolls, semi-dry calender rolls, and the like.
In the stain inhibitor composition of the present embodiment, the drying roller is made of cast iron, but may be made of other materials.
[ examples ] A method for producing a compound
(examples and comparative examples)
The samples of examples 1 to 31 and comparative examples 1 to 9 were prepared by dispersing the active ingredients (linear polysiloxane compound and cyclic siloxane compound) having the structures and the amounts to be blended as described in table 1 below in water. The linear polysiloxane compound used was the compound represented by formula (1), and the cyclic siloxane compound used was a mixture of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in equal amounts.
(evaluation 1)
10ml of the samples obtained in examples 1 to 31 and comparative examples 1 to 9 were prepared, 0.5g of the resin was added, and the degree of dispersion of the resin at this time was visually evaluated.
The resin composition was evaluated as "excellent" when 5 or more resins were dispersed, as "good" when 3 or more and less than 5 resins were dispersed, and as "poor" when 0 or more and less than 3 resins were dispersed.
The results obtained are shown in table 1.
(evaluation 2)
Samples obtained in examples 1 to 31 and comparative examples 1 to 9 were set to 400. mu.g/m2The method (3) was applied to a drying roll of a paper machine, and the adhesion of the drying roll to the surface after 1 hour was visually evaluatedContamination of the resin.
The state of no contamination on the surface of the drying roller was evaluated as "excellent", the state of less than 1 to no contamination on the entire surface of the drying roller was evaluated as "good", the state of 1 to more than 3 to no contamination on the entire surface of the drying roller was evaluated as "Δ", and the state of 3 to more than contamination on the entire surface of the drying roller was evaluated as "x". Note that, if the above evaluation is "excellent", "good", or "Δ", it is considered that the contamination preventive composition exerts the contamination preventive effect.
The results obtained are shown in table 1.
(Table 1)
Figure BDA0002409029970000141
Figure BDA0002409029970000151
Figure BDA0002409029970000161
Figure BDA0002409029970000171
Figure BDA0002409029970000181
From the results shown in table 1, it is understood that the samples of examples 1 to 31 are excellent in the degree of dispersion of the resin and can sufficiently suppress the contamination of the drying roller as compared with the samples of comparative examples 1 to 9.
From this, it was found that the stain inhibitor composition of the present invention can effectively prevent the occurrence of resin staining of the dry part.
[ industrial applicability ]
The anti-staining agent composition of the present invention is used by being applied to a drying section in a papermaking process. According to the stain inhibitor composition of the present invention, the occurrence of resin staining in the drying section can be effectively prevented, and therefore, the yield in the paper making process can be greatly improved.
Description of the reference numerals
B: half-dry calender roll
C: calender roll
D: drying section
D1, D2, D3, D4, D5, D6, D7, D8: drying roller
K1, K2: canvas
KR: canvas roller
W: and (3) wet paper.

Claims (9)

1. A stain inhibitor composition for preventing resin staining in a drying section of a papermaking process,
comprises the following components:
a linear polysiloxane compound represented by the following formula (1); and
a cyclic siloxane compound.
[ CHEM 1 ]
Figure FDA0002409029960000011
[ in the formula (1), the substituent R1The siloxane compound is characterized in that the siloxane compound represents a hydrogen atom, an alkyl group, a methylphenyl group, a polyether group, a higher fatty acid ester group, an amino modified group, an epoxy modified group, a carboxyl group, a phenol group, a mercapto group, a carbinol group or a methacrylic group in the same molecule, and the number n of the repeating units of the siloxane unit represents an integer of 20-1430.]
2. The contamination preventive composition according to claim 1,
the substituents R in the same molecule1At least one of which is an amino-modifying group,
the amino-modified group is represented by the following formula (2).
[ CHEM 2 ]
Figure FDA0002409029960000012
[ in the formula (2), the substituent R2And a substituent R3Each independently represents an alkylene group having 1 to 6 carbon atoms, and the number m of repeating units of the aminoalkylene group represents an integer of 0 to 2.]
3. The contamination preventive composition according to claim 1 or 2,
the cyclic siloxane compound is at least one selected from the group consisting of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
4. The contamination preventive composition according to any one of claims 1 to 3,
the amount of the cyclic siloxane compound is 15ppm to 20000 ppm.
5. The contamination preventive composition according to any one of claims 1 to 4,
the mass ratio of the cyclic siloxane compound to the polysiloxane compound is 1: 5-50000.
6. The contamination preventive composition according to any one of claims 1 to 5,
is an emulsion which also contains an emulsifier and water,
the median particle size of the emulsion is 0.01-5.0 μm.
7. The contamination preventive composition according to any one of claims 1 to 6,
applied to a drying roller made of cast iron or a canvas made of polyester in the drying section,
the absolute value of the Zeta potential is 10-90.
8. The contamination preventive composition according to any one of claims 1 to 7,
is applied to a drying roller consisting of cast iron in the drying section,
the surface tension is below 65mN/m,
the contact angle with the drying roller is below 80 degrees.
9. The contamination preventive composition according to any one of claims 1 to 8,
is applied to a canvas made of polyester in the drying part,
the surface tension is below 65mN/m,
the contact angle between the canvas and the canvas is below 80 degrees.
CN202080000256.6A 2019-03-29 2020-01-16 Pollution preventive composition Active CN112020582B (en)

Applications Claiming Priority (3)

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